JP4944576B2 - Resin composition - Google Patents

Description

  The present invention is characterized in that the organically treated layered silicate is distributed and dispersed with a fluorine compound, and further by adding an anti-drip agent, the resin containing petroleum-derived resin and plant-derived resin is reinforced with flame retardancy. It is related with the made resin composition.

  Resin products are required to be materials that do not place a burden on the environment due to processing problems after use, and conversion to environmentally-adaptive materials is desired. In such a background, resin materials that are recycled and used are conventionally halogen-based, phosphoric acid-based, phosphazene-based, metal compound-based and silicone-based materials in order to maintain flame retardancy that is particularly susceptible to deterioration. Flame retardants such as have been used alone or in combination.

  Among flame retardants, halogen-based flame retardants have a high flame retardant effect, and therefore can exhibit flame retardancy with a relatively small amount of addition. For this reason, when it is recycled and used, there is relatively little decrease in moldability and mechanical strength of the molded product. However, when halogen-based flame retardants are used, a large amount of halogen-based gas is generated during molding and combustion, and the generated halogen-based gas corrodes equipment and adversely affects the human body. There is a fear. For this reason, establishment of a flame retardant method that does not use a halogen-based flame retardant, that is, a so-called non-halogen flame retardant method is strongly desired from the viewpoint of safety.

  As a flame retardant method not using a halogen flame retardant, a method of adding a phosphorus flame retardant to a resin instead of a halogen flame retardant has been reported. However, even when using a method of adding a phosphorus-based flame retardant, depending on the combustion conditions, toxic gas such as phosphine is generated during combustion, or the water resistance of the phosphorus-based flame retardant is low. There is a possibility of environmental impact on water quality.

  For this reason, in recent years, in the electronic equipment field, a flame retardant resin to which a halogen-based flame retardant or a phosphorus-based flame retardant is not added has been developed. As one of the non-halogen flame retardant method and the non-phosphorus flame retardant method, there is a method of adding a metal compound such as aluminum hydroxide, magnesium hydroxide or basic magnesium carbonate which does not generate a toxic gas during combustion. However, the flame retardant effect due to the addition of metal hydroxide is lower than that of halogen flame retardants or phosphorus flame retardants. For this reason, a large amount of addition is required, and as a result, the mechanical strength of the material is lowered and may not be practically used.

  In recent years, silicone flame retardants have attracted attention as flame retardants that do not contain halogen or phosphorus and can be blended into a wide range of resins and have high safety (for example, see Patent Document 1). However, when only the silicone-based flame retardant is added, the oxygen index is greatly improved, but a strong non-combustible film cannot be formed as a continuous layer during actual combustion, and the fire spread cannot be stopped.

  In addition, since the current petroleum-derived resin uses a large amount of various additives such as flame retardants, it is difficult to shift to a material with a low environmental load. In addition, environmentally friendly plant-derived resins generally have lower physical properties such as flame retardancy and mechanical properties than petroleum-derived resins. For this reason, in order to improve the quality, it is essential to prescribe a large amount of additives and materials that can reduce the ratio of plant-derived components (plant degree) to 50%. In addition, nanocomposite materials related to flame retardancy are still under development.

JP 2003-160724 A

  The present invention has been made in view of the above-described state of the art, and an object thereof is to provide a resin composition having low environmental impact and excellent flame retardancy.

（一般式（１）において、ｎは２以上、４以下の整数であり、ｍは２以上の整数である。）

（一般式（２）において、ｎは２以上、４以下の整数であり、ｍは２以上の整数である。） The resin composition of the present invention that has solved the above problems is a resin composition containing a resin, an organically treated layered silicate, a fluorinated alkyl ester polymer, and an anti-drip agent ,
With respect to 100 parts by mass of the resin, the organically treated layered silicate is 0.5 parts by mass or more and 30 parts by mass or less, the fluorinated alkyl ester polymer is 0.001 part by mass or more and 2.0 parts by mass or less and Containing 0.05 parts by mass or more and 0.75 parts by mass or less of an anti-drip agent,
The resin is at least one of compounds represented by the following general formula (1) or the following general formula (2).

(In general formula (1), n is an integer of 2 or more and 4 or less, and m is an integer of 2 or more.)

(In general formula (2), n is an integer of 2 or more and 4 or less, and m is an integer of 2 or more.)

  According to the present invention, an organically treated layered silicate can be easily dispersed in a resin by adding a small amount of a fluorine compound. Further, by adding an anti-drip agent, the flame retardancy of the obtained resin composition can be enhanced by a synergistic effect with the fluorine compound as a dispersant. Thereby, the usage-amount of the layered silicate of a flame retardant can be reduced significantly.

The present invention will be described below with reference to preferred embodiments.
The resin composition of the present invention comprises a resin, an organically treated layered silicate, a fluorine compound, and an anti-drip agent. The resin composition of the present invention comprises 0.5 to 30 parts by mass of the organically treated layered silicate, 0.001 to 2.0 parts by mass of the fluorine compound, and 0 drip inhibitor 0 with respect to 100 parts by mass of the resin. It is preferable to contain 0.05-0.75 mass part.

  Although the said resin used in this invention is not specifically limited, The homopolymer or copolymer represented by the following general formula (1) or (2) is used suitably.

(In the formula, n represents an integer of 2 or more and 4 or less, and m represents an integer of 2 or more.)

(In the formula, n represents an integer of 2 or more and 4 or less, and m represents an integer of 2 or more.)

  Examples of the resin represented by the general formula (1) include petroleum-derived resins such as polyethylene terephthalate (sometimes referred to as PET), polytrimethylene terephthalate (sometimes referred to as PTT), polybutylene terephthalate ( And polyester resins such as PBT). Moreover, as resin represented by the said General formula (2), it represents a plant origin resin obtained by superposing | polymerizing the monomer manufactured using the raw material obtained from biomass, and represents polyethylene flange carboxylate (PEF). And polyester resins such as polytrimethylene furandicarboxylate (sometimes referred to as PTF) and polybutylene furandicarboxylate (sometimes referred to as PBF). For PET, MA-1340P and MA-1344P (both trade names) manufactured by Unitika Ltd. are used, and for PBT, Toraycon 1401 series (X04, X06-08, X31-34, 36, 40 manufactured by Toray Industries, Inc.) 41, X22, E01; trade name), PBT, (Pokan; trade name) manufactured by Bayer Co., Ltd., and the like. However, it is not limited to these.

  The layered silicate used in the present invention is a layered silicate having an exchangeable cation. The layered silicate used in the present invention is not particularly limited. For example, smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, swelling mica, bentonite and the like. Is mentioned. Of these, bentonite, montmorillonite, and swelling mica are preferable. The layered silicate may be a natural product or a synthetic product. Moreover, these layered silicates may be used independently and 2 or more types may be used together.

  The exchangeable cation existing between the crystal layers of the layered silicate is, for example, a metal ion such as sodium or calcium having a cation exchange property with a cationic substance existing on the crystal surface. Since these metal ions have cation exchange properties with a cationic substance, various cationic substances can be trapped between the crystal layers of the layered silicate.

  In the present invention, a so-called organically treated layered silicate obtained by treating the above layered silicate with a cationic substance such as a cationic surfactant or a hindered amine compound in advance is used. The cationic surfactant and the hindered amine compound are captured in the layered silicate that has been subjected to the organic treatment, between the crystal layers and on the surface. In this way, by making it organic and hydrophobizing and preliminarily hydrophobizing the crystal layer and surface of the layered silicate, the affinity between the layered silicate and the resin is increased, and the layered silicate is more uniformly distributed in the resin. Can be finely dispersed. Cationic substances such as the above-mentioned cationic surfactants and hindered amine compounds may be used alone or in combination of two or more.

  The cationic surfactant that can be used in the present invention is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Among them, a quaternary ammonium salt (alkyl ammonium ion) having an alkyl chain having 6 or more carbon atoms is preferably used because it can sufficiently depolarize the crystal layer of the layered silicate.

  Examples of the quaternary ammonium salt include trimethyl stearyl ammonium salt, trioctyl ammonium salt, dimethyl stearyl benzyl ammonium salt, dimethyl dioctadecyl ammonium salt, oleyl bis (2-hydroxyethyl) methyl ammonium salt, and the like. These quaternary ammonium salts may be used alone or in combination of two or more.

  Examples of the quaternary phosphonium salt include dimethyl distearyl phosphonium salt, tributyl hexadecyl phosphonium salt, tributyl dodecyl phosphonium salt, trimethyl lauryl phosphonium salt, trimethyl stearyl phosphonium salt, triphenylmethyl phosphonium salt, trioctyl methyl phosphonium salt. , Triphenyldodecylphosphonium salt, distearyl dibenzylphosphonium salt and the like. These quaternary phosphonium salts may be used alone or in combination of two or more.

  Examples of the hindered amine compound include hindered amine compounds having a 2,2,6,6-tetramethylpiperidine skeleton, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate (Sanol LS770). , Trade name, Sankyo Corporation), bis- [N-methyl-2,2,6,6-tetramethyl-4-piperidinyl] sebacate, bis- [1,2,2,6,6-pentamethyl-4 -Piperidinyl] -2- (3,5-di-tetra-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarbonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarbonate, (Xoxide 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarbonate, Moxide 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarbonate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2 , 2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] (CHIMASSORB 944LD, trade name, Ciba Specialty Chemicals) ), Dimethyl succinate polymer-4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, moxide {2,2,6,6-teto Methyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4 -Butanetetracarboxylate, moxide {2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [4,8,10-tetraoxaspiro ( 5,5) Undecane] diethyl} -1,2,3,4 tetrabutyrate. These hindered amine compounds may be used alone or in combination of two or more.

The organic treatment of the layered silicate can be performed, for example, as follows.
A layered silicate dispersion is prepared by mixing 100 parts by weight of water with layered silicate (0.1-5) parts by weight. Separately, quaternary ammonium compound (5-15) parts by mass are added to 100 parts by mass of water to prepare an aqueous quaternary ammonium compound solution. Next, the quaternary ammonium compound aqueous solution is added to the silicate dispersion so that the quaternary ammonium compound (8 to 50) parts by mass is added to 100 parts by mass of the layered silicate. And it heats to 50-70 degreeC, and stirs for (50-100 minutes), and performs the organication process of a layered silicate. After completion of the organic treatment, this is filtered and washed to remove the remaining quaternary ammonium compound. This is dried at (60 to 100) ° C. (3 to 6 hours) and pulverized to prepare a layered silicate composition (layered silicate subjected to organic treatment). The obtained organically treated layered silicate usually contains (6-46) parts by mass of a quaternary ammonium compound with respect to 100 parts by mass of the layered silicate.

Alternatively, a commercially available layered silicate that has been subjected to an organic treatment may be used.
Commercially available layered silicates that can be used in the present invention include, for example, Organite T (trade name, manufactured by Hojun Co., Ltd.), Sven, Sven NO12, Sven NO12S (trade name, both ( Hojun Co., Ltd.), Somasifu MTE (trade name, manufactured by Coop Chemical Co., Ltd.), Micromica MK-100 (trade name, manufactured by Coop Chemical Co., Ltd.), Kunipia D, Kunipia T (trade name, Kunimine Industries, Ltd.) )) And the like.

  The above-mentioned organically treated layered silicate or commercially available organically treated layered silicate is removed by washing or the like of cationic substances such as cationic surfactants and hindered amine compounds used in the organicizing treatment. It is preferable that When such an organically treated layered silicate is used, when a fluorine compound such as a fluorosurfactant described later is added, the dispersibility of the layered silicate can be markedly increased and the combustion time can be increased. With this shortening effect, the effect of imparting flame retardancy can be enhanced.

  The amount of the organically treated layered silicate is usually preferably 0.5 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the resin. When the blending amount is 0.5 parts by mass or more, a flame retardant film is easily formed, and the flame retardant effect is sufficient. Moreover, when it is 30 mass parts or less, the density of the resin composition obtained does not become high too much, and it has sufficient softness | flexibility, and is preferable.

  The fluorine compound used in the present invention is not particularly limited, but is preferably a fluorine compound having flame retardancy. The fluorine compound used in the present invention is preferably, for example, a fluorinated alkyl ester polymer, and the fluorinated alkyl ester polymer is more preferably a fluorosurfactant.

The fluorosurfactant is not particularly limited. For example, as described in JP-A No. 2003-251166, a perfluoroalkyl such as a trifluoromethyl group, a pentafluoroethyl group, and a heptatrifluorooctyl group is used. Nonionic and cationic fluorine surfactants having a group (C _n F _{2n + 1} —) are preferred. These nonionic and cationic fluorosurfactants may be used alone or in combination of two or more.

  Examples of the nonionic and cationic surfactants used in the present invention include, for example, MegaFuck ESM1 (Nonionic), MegaFuck F178RM (Nonionic), MegaFuck F141 (Nonionic) (trade name, Dainippon Ink and Chemicals, Inc.) Industrial Co., Ltd.), Aftergent 300 (cationic), Aftergent 310 (cationic), Aftergent 100 (anionic) (trade name, manufactured by Neos), Surflon KH-40 (nonionic), Surflon S-121 (cationic), Surflon S-145 (nonionic) (trade name, manufactured by Seimi Chemical Co., Ltd.), Florard FC-170 (trade name, manufactured by Sumitomo 3M Limited), Ftop EF122B (nonionic) System), Ftop EF132 (cation system) (trade name, manufactured by Gemco Co., Ltd.), etc. It is preferably used but not limited thereto.

  These can be used in any form of liquid and solid. However, a powder is preferable because it can be easily used in the blending process and easily mixed with the resin material or the organically treated layered silicate. Both nonionic and cationic fluorosurfactants are effective, but nonionic is more effective and more preferable.

  The fluorine compound is preferably blended in an amount of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the resin. Flame retardance is improved when the blending amount shown on the left is used. When the blending amount is 0.001 part by mass or more, it is easily and uniformly dispersed and flame retardancy is improved. Moreover, combustion time can be shortened if a compounding quantity shall be 2.0 mass parts or less. Furthermore, in order to obtain a stable combustion time shortening effect, the blending amount is preferably 0.01 to 0.25 parts by mass.

  The anti-drip agent used in the present invention effectively prevents the molten resin composition from dropping (drip) by improving the melt viscosity of the molten resin composition at the time of combustion, and has the effect of preventing the spread of fire. Can be granted. Furthermore, this prevents the formation of a sintered film from the layered silicate during combustion, thereby improving flame retardancy.

  The anti-drip agent is not particularly limited, but it is preferable to use a mixture of polytetrafluoroethylene (sometimes referred to as PTFE) and another polymer (sometimes referred to as PTFE mixture). The more PTFE contained in the PTFE mixture, the more the fluorine substitution amount, the more rigid the molecular structure, and the more difficult it is to aggregate. PTFE is also known to take a fibrous structure and become more rigid by stretching. As the PTFE mixture, for example, a PTFE mixture disclosed in Japanese Patent No. 3272985 (Japanese Patent Laid-Open No. 11-29679) is preferably used. This PTFE mixture was obtained by emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing a PTFE particle dispersion having a particle diameter of 0.05 to 1.0 μm and an organic polymer particle dispersion. Thereafter, it can be obtained by pulverization by coagulation or spray drying. Further, as the anti-drip agent used in the present invention, for example, those that are commercially available as “methabrene A-3000”, “methabrene A-3700”, “methabrene A-3800” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Is preferably used.

  Also, a PTFE mixture obtained by supplying a styrene-acrylonitrile copolymer into a PTFE latex as described in JP-A-9-95583 can be used. As such a PTFE mixture, what is marketed as "Blendex 449" (trade name) by GE Specialty Chemicals is known.

  The PTFE content contained in these anti-drip agents is preferably 10 to 70% by mass from the viewpoint of compatibility between the resin to which the anti-drip agent is added and the anti-drip agent.

  The blending amount of the anti-drip agent is preferably 0.05 to 0.75 parts by mass and more preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the resin. When the blending amount is 0.05 parts by mass or more, good flame retardancy can be expressed. Moreover, when a compounding quantity shall be 0.75 mass part or less, the fall of mechanical strength and the softness | flexibility with respect to a bending can be suppressed.

  In addition, it is preferable that the addition amount of a drip inhibitor is 0.5 mass part or less from a viewpoint of environmental impact. For example, the German environmental label Blue Angel sets an upper limit for the amount of polytetrafluoroethylene added to the resin.

  The manufacturing method of the resin composition of this invention is not specifically limited, For example, there exists the method of mix | blending and mixing each predetermined compounding quantity of resin, layered silicate which carried out the organic treatment, a fluorine compound, and an anti-drip agent directly. Also, after preparing a masterbatch by blending the resin with a layered silicate and fluorine compound that have been treated with an organic compound in a prescribed amount or more, and preparing a masterbatch, the resin and drip prevention should be applied to the masterbatch. A so-called master batch method, in which an agent is added and diluted, is mentioned.

  The mixing method in producing the resin composition of the present invention is not particularly limited, and various methods can be used. Examples thereof include a method in which a resin, an organically treated layered silicate, a fluorine compound, and an anti-drip agent are melt-kneaded with an extruder, a two-roll, a Banbury mixer, or the like.

Hereinafter, the present invention will be described more specifically with reference to examples.
However, the present invention is not limited to the following examples, and it goes without saying that various modifications can be made without departing from the spirit of the present invention. In addition, “part” in the present example represents “part by mass” unless otherwise specified.

(Production Example 1) Production of PEF A 1 L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-cooling tube, a thermometer, and a SUS stirring blade was prepared. To this four-necked flask, 2,5-furandicarboxylic acid (149.9 g) and distilled ethylene glycol (186.2 g molar ratio = 1: 3), tin catalyst (monotin oxide Wako Pure Chemical Industries) ( 0.05% by mass (percentage based on the total mass of all materials added), titanium catalyst dissolved in toluene (butyl titanate Kishida Chemical) (0.05% by mass (total mass of all materials added) The base percentage)) was taken.
Stirring was started while introducing nitrogen into the four-necked flask, and the contents were immersed in an oil bath at 150 ° C. to raise the temperature. By the time the internal temperature reached 150 ° C., the by-product water started to flow out along with the condensation reaction, and the temperature was raised to 280 ° C. over about 4 hours.
The fractionating tube was changed to a T-tube and decompression was started. The reaction was continued at about 390 minutes under reduced pressure (5 Pa) at 280 ° C. for about 390 minutes. The obtained polymer was dissolved in a mixed solvent of 1,1,2,2-tetrachloroethane / phenol and reprecipitated with methanol, and then vacuum-dried at 60 ° C. for one day and night. Subsequently, solid state polymerization was performed at a reaction temperature of 180 ° C. in order to increase the molecular weight. The obtained resin was melt kneaded at a cylinder temperature of 190 ° C. with a twin-screw extruder (Laboplast Mill (trade name): manufactured by Toyo Seiki Seisakusho, screw diameter: φ26, L / D = 25), extruded, The strand was cooled and then pelletized using a pelletizer to obtain resin pellets.

(Production Example 2) Production of PBF A 1 L four-necked flask equipped with a nitrogen introduction tube, a fractionation tube-cooling tube, a thermometer, and a SUS stirring blade was prepared. This four-necked flask was charged with 2,5-furandicarboxylic acid (154.0 g) as the dicarboxylic acid and distilled 1,4-butanediol (270.3 g; molar ratio = 1: 3) as the diol. . Furthermore, tin catalyst (monotin oxide Wako Pure Chemical Industries) (0.059% by mass (percentage based on the total mass of all materials added), titanium catalyst dissolved in toluene (butyl titanate kida chemistry) (0. 059% by weight (percentage based on the total weight of all the materials charged)).
Stirring was started while introducing nitrogen into the four-necked flask, and the contents were immersed in an oil bath at 150 ° C. to raise the temperature. By the time the internal temperature reached 150 ° C., outflow of by-product water accompanying the condensation reaction began. Further, the temperature was raised to 170 ° C. over about 4 hours to carry out the condensation reaction.
The fractionating tube was changed to a T-tube and decompression was started. The reaction was continued for about 390 minutes at 180 ° C. under reduced pressure (5 Pa).
The obtained resin was melt kneaded at a cylinder temperature of 190 ° C. with a twin-screw extruder (Laboplast Mill (trade name): manufactured by Toyo Seiki Seisakusho, screw diameter: φ26, L / D = 25), extruded, The strand was cooled and then pelletized using a pelletizer to obtain resin pellets.

Production Example 3 Production of PTF A 1 L four-necked flask equipped with a nitrogen introduction tube, a fractionation tube-cooling tube, a thermometer, and a SUS stirring blade was prepared. To this four-necked flask, 2,5-furandicarboxylic acid (149.9 g), distilled 1,3-propanediol (228.3 g molar ratio = 1: 3), tin catalyst (monotin oxide, Wako Pure) Pharmaceutical industry) (0.05% by mass (percentage based on the total mass of all input materials)), titanium catalyst dissolved in toluene (butyl titanate Kishida chemistry) (0.05% by mass (all input materials) The percentage based on the total mass))) was taken.
Stirring was started while introducing nitrogen into the four-necked flask, and the contents were immersed in an oil bath at 150 ° C. to raise the temperature. Byflow of by-product water accompanying the condensation reaction started when the internal temperature reached 150 ° C., and the temperature was raised to 230 ° C. over about 4 hours.
The fractionating tube was changed to a T-tube and decompression was started. The reaction was continued for about 390 minutes at 230 ° C. under reduced pressure (5 Pa) under full vacuum (5 Pa) over about one hour. The obtained polymer was dissolved in a mixed solvent of 1,1,2,2-tetrachloroethane / phenol and reprecipitated with methanol, and then vacuum-dried at 60 ° C. for a whole day and night. Mw of the obtained polymer was 16400, Tm was 150 ° C., Tg was 39 ° C., crystallization temperature was 102 ° C., and thermal decomposition temperature was 335 ° C.
The obtained resin (polymer) was melt kneaded at a cylinder temperature of 190 ° C. with a twin-screw extruder (laboplast mill (trade name): manufactured by Toyo Seiki Seisakusho, screw diameter: φ26, L / D = 25). After extruding and cooling the strand, it was pelletized using a pelletizer to obtain resin pellets.

Example 1
Resin (sometimes referred to as “A” component), organically treated layered silicate (sometimes referred to as “B” component), fluorine compound (sometimes referred to as “C” component) and anti-drip agent (sometimes referred to as “D” component) The following raw materials were prepared.
Component A: 100 parts [PET resin (trade name “MA-1340P” manufactured by Unitika Ltd.)]
Component B: 5 parts [Montmorillonite treated with trimethylammonium salt (trade name “Organite T” manufactured by Hojun Co., Ltd.)]
C component: 0.1 part [nonionic fluorine surfactant (manufactured by Dainippon Ink & Chemicals, trade name “Megafac EMS1”)]
D component: 0.1 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name “Metabrene 3800”, PTFE content 50 mass%)]

  The raw materials of the above components are fed to an extruder (trade name “TEX30” manufactured by Nippon Steel Works, Ltd.), melt kneaded at a set temperature of 240 ° C., and extruded to prepare a strand of a resin composition. Was pelletized with a pelletizer to obtain resin composition pellets. The obtained resin composition pellets are put into an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., trade name “FN1000-5ADN”), and a sample for UL test V test evaluation is molded at an injection temperature of 250 ° C. ,evaluated. A sample having a length of 127 mm, a width of 12.7 mm, and a thickness of 2.3 mm was prepared as a V test evaluation sample.

(Example 2)
The following were prepared as raw materials for components A to D.
A component: 100 parts [PBT resin (made by Toray Industries, Inc., trade name "Toraycon 1401 X04")]
Component B: 5 parts [Montmorillonite treated with dimethylstearylbenzylammonium salt (trade name “Esben”, manufactured by Hojun Co., Ltd.)]
C component: 0.1 part [nonionic fluorine surfactant (manufactured by Dainippon Ink and Chemicals, trade name “Megafac F178RM”)]
D component: 0.1 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "Metabrene 3700", PTFE content 20% by mass)
A sample for evaluation was molded and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were the above.

(Example 3)
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PEF prepared in Production Example 1]
Component B: 5 parts [Montmorillonite treated with oleylbis (2-hydroxyethyl) methylammonium salt (trade name “Esven NO12S” manufactured by Hojun Co., Ltd.)]
C component: 0.1 part [nonionic fluorine surfactant (manufactured by Dainippon Ink & Chemicals, trade name “Megafac 141”)]
D component: 0.2 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000", PTFE content 20 mass%]
A sample for evaluation was molded and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were as described above and that the amount of component D was 0.2 part.

Example 4
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PBF prepared in Production Example 2]
Component B: 5 parts [Montmorillonite treated with dimethylstearylbenzylammonium salt + oleylbis (2-hydroxyethyl) methylammonium salt (trade name “Esven No12” manufactured by Hojun Co., Ltd.)]
C component: 0.1 part [cationic fluorine surfactant (manufactured by Neos Co., Ltd., trade name “Fargent 300”)]
D component: 0.2 parts [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name “Metabrene 3700”)]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials of components A to D were as described above, and the amount of component D was 0.2 part.

(Example 5)
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PTF prepared in Production Example 3]
Component B: 5 parts [Mica treated with dimethylstearylbenzylammonium salt + oleylbis (2-hydroxyethyl) trioctylmethylammonium salt (trade name “Somasifu MTE”, manufactured by Corp Chemical Co., Ltd.)]
C component: 0.1 part [nonionic fluorine surfactant (made by Sey Chemical Co., Ltd., trade name “Surflon KH-40”)]
D component: 0.3 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for the components A to D were as described above, and the amount of the component D was 0.3 parts.

(Example 6)
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PEF prepared in Production Example 1]
Component B: 5 parts [Montmorillonite treated with oleylbis (2-hydroxyethyl) methylammonium salt (trade name “Esven NO12S” manufactured by Hojun Co., Ltd.)]
Component C: 0.1 part [Anionic fluorine surfactant (manufactured by Neos Co., Ltd., trade name “Furgent 100”)]
D component: 0.2 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "Metabrene 3800")
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for the A to C components were as described above and the blending amount of the D component was 0.2 parts.

(Example 7)
The following were prepared as raw materials for components A to D.
A component: 100 parts [PBT resin (made by Toray Industries, Inc., trade name "Toraycon 1401 X04")]
Component B: 5 parts [Organized mica treated with tributyl dodecyl phosphonium salt (Organized mica manufactured by Corp Chemical Co., Ltd., trade name “Micro Mica MK-100”), organic with tributyl dodecyl phosphonium salt] )
C component: 0.1 part [cationic fluorine surfactant (manufactured by Neos Co., Ltd., trade name “Furgent 300”)]
D component: 0.1 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name “Metabrene 3700”)]
A sample for evaluation was prepared and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were the above.

(Example 8)
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PEF prepared in Production Example 1]
Component B: 5 parts [Mica treated with tributylhexadecylphosphonium salt (organized mica manufactured by Corp Chemical Co., Ltd., trade name “Micromica MK-100”, tributylhexadecylphosphonium salt) Organically treated))]
C component: 0.1 part [nonionic fluorine surfactant (made by Sey Chemical Co., Ltd., trade name “Surflon S-121”)]
D component: 0.2 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were as described above, and the amount of component D was 0.2 parts.

Example 9
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PBF prepared in Production Example 2]
Component B: 5 parts [Montmorillonite organically treated with dimethylstearylbenzylammonium salt + oleylbis (2-hydroxyethyl) methylammonium salt (Kunimine Kogyo Co., Ltd., trade name “Kunipia D”)]
C component: 0.1 part [nonionic fluorine surfactant (made by Sey Chemical Co., Ltd., trade name “Surflon S-121”)]
D component: 0.2 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were as described above, and the amount of component D was 0.2 parts.

(Example 10)
The following were prepared as raw materials for components A to D.
Component A: 100 parts [PTF prepared in Production Example 3]
Component B: 5 parts [Montmorillonite organically treated with trimethylalkylammonium salt (Kunimine Kogyo Co., Ltd., trade name “Kunipia T”)]
C component: 0.1 part [cationic fluorine surfactant (manufactured by Neos Co., Ltd., trade name “Fargent 300”)]
D component: 0.3 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for components A to D were as described above, and the amount of component D was 0.3 parts.

(Comparative Example 1)
The following were prepared as raw materials for the C component.
Component C: 0.1 part [anionic fluorine surfactant (manufactured by Dainippon Ink & Chemicals, trade name “Megafac 114”)]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for component C were as described above and that component D was not blended.

(Comparative Example 2)
The following were prepared as raw materials for the A component and the B component.
A component:
[PBT resin (made by Toray Industries, Inc., trade name “Toraycon 1401 X04”)]
B component:
[Montmorillonite organically treated with dimethylstearylbenzylammonium salt (manufactured by Hojun Co., Ltd., trade name "Esben")]
A sample for evaluation was prepared and evaluated in the same manner as in Example 1 except that the raw materials of the A component and the B component were as described above, and the C component and the D component were not blended.

(Comparative Example 3)
Instead of montmorillonite (trade name “Esven”, manufactured by Hojun Co., Ltd.), which is obtained by organizing the raw material of component B with trimethylammonium salt, swellable mica (trade name “Micro Mica MK-100” manufactured by Corp Chemical Co., Ltd.) Except for the above, an evaluation sample was prepared and evaluated in the same manner as in Example 1.

(Comparative Example 4)
The following were prepared as raw materials for the A and D components.
Component A: 100 parts [PBF prepared in Production Example 2]
D component: 0.2 parts [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name “Metabrene 3700”)]
Evaluation was performed in the same manner as in Example 1 except that the raw materials for the A and D components were as described above, the B component and the C component were not blended, and the blending amount of the D component was 0.2 parts. Samples were prepared and evaluated.

(Comparative Example 5)
The following were prepared as raw materials for the A component, the C component, and the D component.
Component A: 100 parts [PTF prepared in Production Example 3]
C component: 0.1 part [nonionic fluorine surfactant (manufactured by Dainippon Ink and Chemicals, trade name “Megafac F178RM”)]
D component: 0.2 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
In the same manner as in Example 1, except that the raw materials of the A component, the C component, and the D component were as described above, the B component was not blended, and the blending amount of the D component was 0.2 part. An evaluation sample was prepared and evaluated.

(Comparative Example 6)
The following were prepared as raw materials for the C component.
Component C: 0.1 part [anionic fluorine surfactant (manufactured by Dainippon Ink & Chemicals, Inc., trade name “Megafuck 116”)]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for component C were as described above, and components B and D were not blended.

(Comparative Example 7)
The following were prepared as raw materials for the A component and the B component.
A component: 100 parts [PBT resin (made by Toray Industries, Inc., trade name "Toraycon 1401 X04")]
Component B: 5 parts [Montmorillonite treated with dimethylstearylbenzylammonium salt + oleylbis (2-hydroxyethyl) methylammonium salt (trade name “Esven No12” manufactured by Hojun Co., Ltd.)]
Samples for evaluation were prepared and evaluated in the same manner as in Example 1 except that the raw materials for the A component and the B component were as described above and the C component was not blended.

(Comparative Example 8)
The following were prepared as raw materials for the A and D components.
Component A: 100 parts [PEF prepared in Production Example 1]
D component: 0.3 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
In the same manner as in Example 1 except that the raw materials of the A component and the D component were as described above, the B component and the C component were not blended, and the blending amount of the D component was 0.3 part, An evaluation sample was prepared and evaluated.

(Comparative Example 9)
The following were prepared as raw materials for the A component and the C component.
Component A: 100 parts [PBF prepared in Production Example 2]
C component: 0.1 part [nonionic fluorine surfactant (manufactured by Dainippon Ink & Chemicals, trade name “Megafac 141”)]
A sample for evaluation was prepared and evaluated in the same manner as in Example 1 except that the raw materials of the A component and the C component were as described above, and the B component and the D component were not blended.

(Comparative Example 10)
The following were prepared as raw materials for the A component, the C component, and the D component.
A component:
[PTF prepared in Production Example 3]
C component: 0.1 part [cationic fluorine surfactant (manufactured by Neos Co., Ltd., trade name “Fargent 300”)]
D component: 0.3 part [Anti-drip agent (Mitsubishi Rayon Co., Ltd., trade name "METABRENE 3000")]
In the same manner as in Example 1 except that the raw materials of the A component, the C component, and the D component were as described above, the blending amount of the D component was 0.3 part, and the B component was not blended. An evaluation sample was prepared and evaluated.

  The performance of the samples for evaluation obtained in the above examples and comparative examples was evaluated by the following methods. The obtained evaluation results are shown in Tables 1 and 2.

(Average interlayer distance of layered silicate)
Using an X-ray diffractometer (trade name “X ′ Pert Pro” manufactured by Pnylytic, Inc.), 2θ of the diffraction peak obtained from diffraction of the layered surface of the organically treated layered silicate in the sample for evaluation was measured. The (001) spacing (d) of the layered silicate was calculated by the following Bragg diffraction formula. The obtained d was defined as the average interlayer distance (nm).
d = λ / 2 sin θ
(In the formula, λ represents the wavelength of X-rays, θ represents the diffraction angle, and d represents the interplanar spacing of the layered silicate.)
Measurement conditions X-ray source CuKα
Incident side 0.04 °
SS / PDS DS = SS = 1
RS = 0.15mm

(Dispersibility of layered silicate layer)
Using a transmission electron microscope (trade name “H800”, manufactured by Hitachi, Ltd.), an electron micrograph of the layered silicate in the sample for evaluation was taken, and the state of the layer of the layered silicate was observed. Based on the obtained results, the dispersibility of the layered silicate layer was evaluated according to the following criteria.
[Criteria]
○: 20% or more of the number of layered silicates had 5 or less layers Δ: 0% or more and less than 20% of the number of layered silicates had 5 or less layers × : All layered silicates had more than 5 layers

(UL94 2.3mmV test)
Flammability was evaluated based on UL94 V-0, V-1, and V-2 standards.
In the above test, those that did not correspond to any of V-0 to V-2 were designated as “NG”.

(Drip resistance)
The drip property was evaluated according to the UL94 standard. The upper part of the test piece (length 127mm x width 12.7mm x thickness 2.3mm) is clamped, the bottom surface of the test piece is ignited, and the surgical cotton placed 20cm directly below the test piece is tested. It was visually observed whether or not it was ignited by the combustion dropout from the combustion test piece, and the drip resistance was evaluated according to the following criteria.
[Criteria]
○: The surgical cotton did not ignite.
X: Surgical cotton ignited.

As shown in Table 1, the resin composition containing a resin (A component), an organically treated layered silicate (B component), a fluorine compound (C component) and an anti-drip agent (D component) The dispersion distance of the layered silicate is large, and the dispersibility of the organically treated layered silicate is also excellent. Moreover, the flame retardancy evaluated by UL94 and the drip resistance are also excellent.
On the other hand, as shown in Table 2, the resin composition lacking any one of the B component, the C component, and the D component is inferior in flame retardancy as compared to the resin compositions of the above examples. It has become a thing.
If it sees in detail, the dispersion distance of the organically processed layered silicate will become large in the resin composition prepared from A component, B component, and C component. Moreover, when the dispersibility of B component improves, it contributes to an improvement in a flame retardance, and also by adding D component, the specification of UL94 V test piece is B component, C component, It improves compared with the thing which does not add any component of D component. Also, drip resistance is improved.

Claims (5)

A resin composition comprising a resin, an organically treated layered silicate, a fluorinated alkyl ester polymer and an anti-drip agent ,
With respect to 100 parts by mass of the resin, the organically treated layered silicate is 0.5 parts by mass or more and 30 parts by mass or less, the fluorinated alkyl ester polymer is 0.001 part by mass or more and 2.0 parts by mass or less and Containing 0.05 parts by mass or more and 0.75 parts by mass or less of an anti-drip agent,
The resin composition is at least one of compounds represented by the following general formula (1) or the following general formula (2).

(In general formula (1), n is an integer of 2 or more and 4 or less, and m is an integer of 2 or more.)

(In general formula (2), n is an integer of 2 or more and 4 or less, and m is an integer of 2 or more.) Wherein the resin is selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene furandicarboxylate, according to claim 1, characterized in that at least one of the polytrimethylene furan dicarboxylate, and polybutylene furan dicarboxylate Resin composition. The resin composition according to claim 1 or 2 , wherein the layered silicate is mica or montmorillonite . The resin composition according to any one of claims 1 to 3 , wherein the fluorinated alkyl ester polymer is a nonionic or cationic fluorosurfactant having a perfluoroalkyl group . The resin composition according to any one of claims 1 to 4 , wherein the anti-drip agent contains polytetrafluoroethylene.